Fiber-reactive fluoroalkyl derivatives of amino-aldehyde compounds and textiles &#34;soil proofed&#34; therewith



United, States Patent 3,296,264 FIBER-REACTIVE FLUOROALKYL DERIVATIVESOF AMINO-ALDEHYDE COMPOUNDS AND TEX- TILES SOIL PROOFED THEREWITHDomenick Donald Gagliardi, East Greenwich, R.I., as-

signor to Colgate-Palmolive Company, New York, N.Y., a corporation ofDelaware No Drawing. Filed Sept. 30, 1963, Ser. No. 312,291 3 Claims.(Cl. 260-249.6)

.The present invention relates to fiber-reactive fluoroalkyl derivativesof heterocyclic amido compounds and to textiles soil proofed therewithand more particularly to fiber-reactive fiuoroalkyl derivatives ofcyclic ureas, triazines and guanamines, compounds and textiles soilproofed with said fluoroalkyl derivatives.

The treatment of textiles including fibers, yarns, woven fabrics, feltedfabrics, and the like has been practiced for many centuries. At firstman was concerned with imparting to textiles the capability ofresistance to wetting by water. Many emperically developed mixtures'have been applied to cloths to provide the water-repelling rainwearwhich has in the'past been known as macintoshes. Everybody is acquaintedwith the coated fabric generally available as oil cloth. These earlycoated fabrics presented'one surface which was a continuous film of thecoating material which filled the interstices of the cloth, changed theporosity of the cloth, and the air permeability of the cloth. It was not'until about 1 935 that there was any attempt to discover the factorscontrolling'resistance to wetting by water. Prior to this time, textilematerials were coated with various cookbook recipes such as rubber,linseed oil-rubber mixtures, emperical and esoteric synthetic dopes andother compositions having no basis in a discovery of the physicalproperties of a preparation which would impart to a textile thecapability of resisting wetting by water or more briefly waterrepellency.

Without understanding the basic principles of the mechanism ofconferring water repellency to textiles such as surface free energy,contact angle, and spreading coefficient several unrelated practicaldevelopments arose during the period from 1935 to 1940 which changed theart of water-proofing textiles. In Germany, a series of paraffin waxemulsions were developed which, when padded onto textiles, produced ahigh contact angle of water drops on the surface and a high degree ofshower resistance without changing the porosity or air permeability ofthe textile material as do the preparations recommended for waterproofing prior to 1935. The fabrics treated with these paraffin-waxemulsions were not wettable by water and water-borne liquids and stainsbecause of the change of the free energy of the fiber surfaces and notbecause the interstices of the woven fabrics were plugged. Thus, apractical improvement was made without an understanding of the reasonfor the advance in the art.

By the use of these new wax emulsion-metallic salts mixtures, it wasthen and is now possible to produce fabrics which have the feel and'apparance of conventional fabrics but do not look like oil-cloths orfabrics having rubberized coating. The only practical limitation of suchmixtures is the durability to washing and drycleaning. This class ofwater-proofing materials generally comprises a mixture containing:

(a) A parafiin wax or mixtures of vegetable wax esters such as carnauba,candelilla, or sugar cane wax.

(b) An emulsifying agent, usually glue, gelatin, and rosin soaps.

(c) An aluminum or zirconium salt, usually the formate or acetate. Theprimary function of the salt is to Patented Jan. 3, 1967 Seeinsolubilize the glue and other emulsifiers after the emulsion isdeposited on the fabric.

A large variety of such products are still in use as low-cost,non-durable water repellants for textiles. Since neither thermosettingnor fiber reaction occurs when textiles are coated with such products,the treated textile is non-durable to washing and dry cleaning. Otherthan water repellency for rainwear fabrics, such mixtures providefabrics with a fair degree of spot and stain resistance to water-bornechromophoric materials.

The search for durable or permanent water repellants as contrasted withthese non-durable water repellants, especially for'cellulosic fibers wasinitiated by the need to overcome the deficiencies of these waxemulsion-metallic salt mixtures. The first major advance occurred inEngland where a product marketed under the trade name Velan wasproduced. This material was octadecyloxymethyl pyridinium chloride, aquaternary ammonium compound made by the chloromethylation ofoctadecanol, followed by quaternization with pyridineto yield a producthaving a composition represented by the formula This compound, unlikeother quaternan'es, is unstable and under acid conditions reacts withsurfaces containing active hydrogen, e.g., the hydrogen of a hydroxylgroup in cellulose fibers. If the cellulose molecules be represented byZ(OH),,' then the reaction can be considered to be summarized by theequation:

z oH ,,+nc,,H,,ocH,NP

. 2 1B 37)n-l-PY Where py is the balance of the pyridine ring. Fabricstreated with such a compound are durably water repellant, are porous,soft, and have the appearance of untreated fabrics. 3

A major improvement of the Velan type material was made when thestearamidomethyl analog of Velan v v n H 0-0 m.

C11H35C ONHCHzEI CH commercially known as ZelanUand Norane R wasproduced. The advantage of the ste-armamide product is greater initialwater repellancy and greater durability to washing. Such products arestill among the forefront of the leaders inrainwear fabric finishes.

In the search for other fabric-reactive or durable water repell'antsother classes of compounds have been developed. Illustrative of theseother classes of water repellants are the silicone water repellantsmethyolstearamide compositions (permel, Ahcovel NW), hydrophobic resins(Norane GG, Raned'are R, Argus DWR, octadecylketene dimer [Aquapel]) andothers.

While durable water repellants had been initially developed forouterwear and raincoat applications, it was soon recognized that durablewater repellants could be used as finishes for other purposes. In theperiod 1950 to 1956 these durable water repellent finishes were widelyused on mens suitings, dress goods, and upholstery materials. Whenoffering these products to the textile finish-v ing trade, promotionalemphasis was not placed on waterrepellency but on spot-and-stainresistance. This use has continued to the present time. It had beenobserved that fabrics treated with such durable water repellants had ahigh degree of resistance to soiling by water-borne soils and stains andwere easier to launder. The primary limitation of these finishes wasthat they attracted rather than repelled oily soils, and the treatedfabrics were not resistant to staining by oily materials such as oils,greases, gravy, mayonnaise, etc.

In the early part of the 1950 decade based on work done at NavalResearch Laboratory by Fox and Zisman and from work done at a divisionof the Minnesota Mining and Manufacturing Co., the utility of certainfluorocarbon based chemicals as fibrous finishes was announced. Fox andZisman had demonstrated the physiochemical principle of low free energysurfaces and the relation of non-wetting with water or oils of surfacestreated with chemicals containing perfluoroalkyl groups.

The practical developments of 3M culminated in the introduction of thefirst product for textile treating. This product is still known as F0449and is a classical Werner complex of a carboxylic acid made by reacting1 mol of the acid with 2 mols of basic chromic chloride.

The compound is water soluble and cationic in nature. It exhibits strongadhesion to anionic substrates such as cellulose and fiberglass. It alsocomplexes with proteinaceous fibers such as wool, silk, and leather togive both water and oil repellant surfaces. It is generally believedthat perfluorodecanoic acid is the base for this product.

Subsequently, 3M made a product known :as FC-208 available as a finish.It is generally believed that this finishing material is aperfluorosulfonamide polymer having a composition corresponding to theformula:

III

[FQC' (CF2)X-SOZ N "-0o-o=0H1]..

where x is an integer in the range of 3 to 13, R is methyl, ethyl,propyl, butyl, amyl, hexyl, R" is an alkylene radical having 1 to 12carbon atoms and R' is hydrogen, methyl, or ethyl.

The advent of these perfluoro finishes produced a great practicalimprovement in fabric finishes. Although of little merit for plain waterrepellency for outerwear purposes, the two products, i.e., the WernerComplex and the perfluorosulfonamide, offer a solution to the problem ofproviding fabrics with water-and-oil repellency and practical resistanceto staining. Because of its hydrolytic instability the Werner complexhas been limited to wool, leather, and upholstery finishes. Thesulfonamide has become a leader in finishes for cotton, rayon, andnoncellulosic synthetic fiber.

Although important for water-and-oil repellency and resistance tostaining by water-and-oil borne stains for wearing apparel, upholsteryand the like, the capability of shedding oily particulate soil is ofgreater importance. That is to say, the finely divided environmentalgrime mixed with the oil exudations of the human skin, i.e., oilyparticulate soil, soil in the neckband and cuffs of a mans shirt, arefar more often encountered than soiling with gravy or mayonnaise. Hence,while fabric finishes which repel water, oil, water-borne and oil-bornestains are of great importance, the capability of resisting staining byoily particulate soil is of greater importance for aesthetic reasons iffor no other reason. Yet even the perfluoro finishes presently availabledo not have the capability of resisting staining by oily particulatesoil. In fact they enhance such soiling.

It is manifest that controlled evaluating of fabric finishes in actualuse is not possible. Consequently, it has been necessary to useevaluation methods subject to laboratory control which will simulate asclosely as possible actual conditions under which water-repellency,oilrepellency, resistance to staining by water-borne and oilbornestains, and resistance to staining by oily particulate soil of treatedfabrics occurs. Such methods of evaluation are the following.

4 WATER REPELLENCY Resistance t0 wetting (spray test) AATCCstandard testmethod 22-1952 This test is applicable to any textile fabric. Itmeasures the resistance of fabrics to wetting by a water spray. and theresults depend primarily on the degree of hydrophobicity inherent in thefibers and yarns and subsequent treatments to which the fabric issubjected. Water is sprayed against the taut surface of a test specimen.Evaluation of the "wetted pattern is readily brought about by comparingthe wetted pattern with standard wetting pattern pictures:

Rating: Characterized by No sticking or wetting of the upper surface. 90Slight random sticking or wetting of the upper surface. 80 c Wetting ofthe upper surface at spray points. 70 Partial wetting of the whole ofthe upper surface. 50 Complete wetting of the whole'of the uppersurface. 0 Complete wetting of the whole of the upper and the lowersurfaces.

The test specimens of minimum size of 7" x 7" (seven inches by seveninches) are conditioned at 70 F. and 65 percent relative humidity for aminimum of four hours before testing.

The test specimen, fastened securely and wrinklefree in a metal hoophaving a diameter of 6 inches, is placed and centered 6 inches under astandard spray nozzle at an angle of 45 to the horizontal. Two hundredand fifty milliliters of water at 8012" F. is poured into a funnelattached above the spray nozzle. The spray lasts 25 to 30 seconds at theend of which time the hoop is taken by one edge and the opposite edgetapped smartly once against a solid object with the wet side facing thesolid; this procedure is repeated with the hoop reversed OIL REPELLENCY3M textile chemicals Appendix Atest methods,

page 1 The Minnesota Mining oil repellency test is based on I thedifferent penetrating properties of the two hydrocarbon liquids, mineraloil (Nujol) and n-heptane.

(Nujol is the tradename for white mineral or paraffin oil being amixture of hydro-carbons having a density for light oil in the range of0.83 to 0.860 and for heavy oil in the range of 0.875 to 0.905). The

Nujol-heptane proportions for each rating were selected by 3M to give.oily stain resistance somewhat comparable to the Water-borne stainresistance corresponding to each of the spray ratings of the AATCCStandard Test Method 22-4952.

Percent Nujol (by volume) Oil Repellency Rating N 0 hold out to Nujol.

The standard oil-heptane mixtures are contained in small stopperedmedicine-dropper bottles. A drop of each mixture of Nujol and heptane isplaced on the fabric.

The appearance of the test oil is observed through the drop. Note ismade whether wetting or penetration occurs. The number corresponding tothat mixture containing the highest percentage of heptane which does notpenetrate or wet the fabric after three minutes is considered the oilrepellency rating of the system.

The change in the optical refractivity of the drop is often anindication of wetting. In some cases wetting can be better determined byobserving the other side of the fabric. In some cases reportedhereinafter the term has been used to indicate a modicum of resistanceto wetting by oil.

STAIN REPELLENCY The following procedures have been used to establishthe degree of resistance to staining by water-borne and oil borne stainsof fabrics.

(a) The fabrics were stretched lightly on 12" x 31 frames. All or, partof the frame was used depending upon the amount of fabric available. Theframes were supported at both ends with the fabric about 8 inches abovea black surface. The fabric touched nothing.

(b) Three inch medicine droppers were used to draw the stains from thecontainers. A l-cubic centimeter calibration was established and markedon the exterior of each'dropper. The stains were squeezed verticallydownward from a height 2 inches above the cloth.

(c) After five minutesthe unabsorbed stain was wiped off the fabric withtwo sweeps of Kleenex and the stains rated as follows:

Appearance: Rating No stain visible -s Slight stain 4 Easily noticeablestain 3 Considerable stain 2 Very heavily stained 1 (The spread or lackof spread is not necessarily reflected inthe ratings).

(d) Duplicate sets of stains were applied in separate areas so thatone-half of the fabric could be washed. In most instances, the wash wascarried out with 50 grams of Fab, a cotton cycle, and a dummy load tototal 5 pounds in a Norge home automatic washer.

(e) The following .twolists describe the numbering and the grosscharacterizations of the stains employed. \Vater stains:

' 1. Instant tea 2. Sheafiers 232 blue-black skrip. 3. A & P Concordgrape juice.

4. Ann Page salad mustard. S. Bosco chocolate syrup.

Oil stains:

6. Wesson oil. 7. Gulf Supreme motor oil 20/ 20. 8. Oleomargarine 9. LaRosa tomato sauce.

10. Jergens lotion.

1 8 cc. dry powder/200 cc. Water a lied at 160" F Melted and applied at160 F pp In reporting the relative resistance to staining and ease ofstain removal in laundering, the staining values for water-borne andoil-borne stains were averaged separately.

In all cases the stains were allowed to dry on the fabrics fortwenty-four hours before laundering.

OILY PARTICULATE SOIL REPELLENCY (GRC dry soil test) Fifteen to twenty6" x 8 numbered specimens (normally 80 x 80 cotton), including at leastone untreated control, are tumbled for thirty minutes with 10 percent of-Cyanamid Soil based on the weight of the fabric. The tumbling iscarried out in a 5-liter capacity Five- Minute Home Cleaner at 44r.p.m.; six No. 8 neoprene 5 rubber stoppers are distributed among thespecimens to increase the mechanical action. At the end of tumbling, thespecimens are removed and each shaken separately up and down fifteentimes by hand to remove surface dirt.

The specimens are then cut in two (to produce two 4" x 6" pieces).One-half is washed with 50 grams of Fab in a cotton cycle with a 5-pounddummy load, then hung to dry and lightly ironed under a clean cottoncloth.

The degree of soiling is determined with a Photovolt Reflectance Meter(Tri Blue Filter). Six readings per specimen are made and the arithmeticaverage reported.

The Cyanamid Soil described below is the same as that recommended byMinnesota Mining and Manufacturing Co. The following dry ingredients areblended thoroughly, dried in a forced draft convection oven for eighthours at 50 C., then milled for twent-five hours with ceramic balls andstored in a polyethylene bag.

CYANAMID SOIL Material: Percent by weight Peat moss 38 Cement 17 Kaolinclay 1 17 Silica, 200 mesh 17 Furnace black 3 1.75

Red iron oxide 4 0.50 Mineral oil 8.75

1 Peerless R. T. Vanderbilt. 2 Davidson Chemical Co.

3 Molacco Benny and Smith C0.

4 C. K. Williams 00.

It has now been discovered that fiber-reactive fluoroalkyl derivativesof amino-aldehyde compounds, i.e.,- fiuoroalkyl' derivatives ofmonocyclic ureas and thioimino compounds having compositionscorresponding to the formula:

where Q is a fluoroalkyl group having four to twelve (inclusive) carbonsatoms in which at least 70 percent to percent of the (2n+1) hydrogenatoms (11:4 to 12) has been replaced by fluorine atoms and at least twoand preferably three fluorine atoms are attached to the terminal oromega carbon atoms; X is 'm is one to five dependent upon thefunctionality of the amide residue; n is at least one; (m+n) is two tosix inclusive; R is a divalent radical selected from the group:

Monocyclic ureas 0 R has the significance given hereinbefore,

where Y and R have the significance :given hereinbefor Triazines Therecan be one (QXCH group or as many as five, depending upon thefunctionality of the amido residue. There must always be at least one(CH OR') group remainin gfor reaction with the fiber, e.g., withcellulose (ZOH) H O OHzC CHzO CH;

CHzOCH;

C CHzOCIIa where Q is CH (CF CF has been prepared by reacting hexa(methoxyrnethyl) melamine and pentadecafluorooctyl alcohol in equimolarproportions using about 0.05 part by weight of 85 percentorthophosphoric acid as the ether interchange catalyst. The reactionmixture was heated from 103 C. to 153 C. in about thirty minutes duringwhich time an amount of methanol was collected indicating thereplacement of one methyl group by the pentadecafiuorooctyl group andthe formation of the pentadecafiuorooctoxymethylpenta (methoxymethyl)melamine. Pentadecafiuorooctoxymethylpenta (methoxymethyl) melamine andthe other fluoroalkyl derivatives of amino-aldehyde compounds within thescope of formula (B) supra are reactive with textile materials havingactive hydrogen atoms in the surfaces thereof.

Equimolar amounts of C trihydroperfiuoroalkyl alcohol (CHF (CF CH OH)and tetramethylolacetylene monourein were condensed using 85 percentphosphoric acid as the condensation catalyst. An amount of water wasstripped indicating the formation of the C trihydroperfluoroalkytrimethylolacetylene monourein.

The C trihydroperfiuoroalkyl, trimethylolacetylene monourein was paddedon 80 x 80 cotton from 3 percent isopropanol solution (Run No. 1) andfrom 3 percent isopropanol solution in the presence of a zinc complex asa catalyst (Run No. 2); The .degree of soil proofing conferred on thetextile is indicated by the values reported in i the following table.

Cured at Room Temperature Percent Run No. Catalyst ReflectanceRepelleneies, Oil

Untreated Cotton: 0 26 77 1 0 80 43 81 2 1. 5 80 36 81 The heterocyclicnitrogen bases of the present invention are not to be confused with whatseems to be similar compositions previously known to the art.

of wetting, detersive, and dispersing agents which may be represented bythe general formula:

N(CHz)n-OH B where R is an alkyl or acyl radical having about five toabout twenty-three carbon atoms, A and B are ethylene radicals, and mand n are integers in the range of two to X (O'O H2n)n \NR where X isR'or R-CO; A and B are unsubstituted ethylene radicals or ethyleneradicals having one to four short chain alkyl substituents of not morethan two carbon atoms; R is a long-chain aliphatic radical such that thecarbon content of X is from six to twenty-four carbon atoms; R is ashort-chain alkyl or acyl radical; and n is 1 to 9, are described. Thesepiperazines are said. to be suitable for softening fabrics, fixingcolors, removing grease and oil, and penetrating and in ore flotation asaddition agents. In other words, these piperazines are" of the nature ofsurfactive agents with no suggestion that such materials when applied totextiles will shed oily particulate soil.

Novel detergents conforming to the general formula:

where R is an alkyl or acyl radical having five to twentythree carbonatoms; A and B are ethylene radicals wherein any number of hydrogenatoms (none, one or more) are replaced by alkyl radicals; and m and nare integers in the range of two to five are disclosed in U.S. PatentNo. 2,634,239. It is trite to remark that detergents are not suggestiveof soil-proofing finishing agents.

What is claimed is:

1. Heterocyclic nitrogen base having the composition corresponding tothe formula (inclusive) carbon atoms in which at least 70 percent topercent of the (2n+1) hydrogen atoms (n=4 to 12) i For example in US.Patent No. 2,421,707 there are disclosed a group 1 9 10 has beenreplaced by fluorine atoms and at least two and Triazines preferablythree fluorine atoms are attached to the termi- N nal or omega carbonatom; X is \fi II 5 N N CNH or \O/ R is hydrogen, CH C H C H m is one tofive dependent upon the functionality of the amido residue; n is atleast 1; (m-l-n) is two to six inclusive, R is a divalent radicalselected from the group 10 Gumammes Monocyclic ureas RC CN Y I ll N N sN where 2. Pentadecafluorooctoxymethylpenta (methoxymeth- --CHgCHzCHz,-CH2OCH2, --CHzI;T-CH

yl) melamine.

R 2 3. C trihydroperfluoroalkyltrimethylolacetylene di- R has thesignificance given hereinbefore, ureine- Diheterocydic areas ReferencesCited by the Examiner UNITED STATES PATENTS T 2,630,433 3/1954 Kaiser eta1. 260-2499 I 2,781,553 2/1957 Varela et al. 18-60 WALTER A. MODANCE,Primary Examiner.

Where Y and R have the significance given hereinbefore FORD, AssistantExamine"-

2. PENTADECAFLUOROOCTOXYMETHYLPENTA (METHOXYMETHYL) MELAMINE.
 3. C11 -TRIHYDROPEFLUOROALKKYLTRIMETHYLOLACETYLENE DIUREINE.